TRIPHENYLBIS (FLUOROALKOXY) PHOSPHORANES AND FLUORINATED KETALS

Abstract: Novel triphenylbis (fluoroalkoxy) phosphoranes and a process for their preparation are disclosed. Also disclosed is a process for making fluorinated ketals by reacting phosphoranes with fluorinated ketones.

Description: JTΣ E TRIPHENYLBIS (FLUOROALKOXY)PHOSPHORANES AND FLUORINATED KETALS FIELD OF THE INVENTION Novel triphenyIbis (fluoroalkoxy)phosphoranes are disclosed. Also disclosed are fluorinated ketals made from these phosphoranes with fluorinated ketones and a process for their preparation. TECHNICAL BACKGRQUNP One triphenyIbis (fluoroalkoxy)phosphorane, PΪ13P (OCH2CF3)2, has been disclosed in the literature. See the following references a-d: a) N. Lowther and C. D. Hall, J. Chem. Soc, Chem. Comm., 1303 (1985) describe the preparation of Ar3P (OCH2CF3)2 (Ar = substituted phenyl rings) by the reaction of Ar n P(OR) n -3 (n = 0 to 3) with PhSOCH2CF3 and the mechanisms in the hydrolysis of these phosphoranes. b) M. Von Itzstein and I. D. Jenkins, Aust, J. Chem., 36, 557 (1983), disclose a method for the preparation of dialkoxytriphenylphosphoranes by the reaction of Ph3P with alcohols in the presence of azodicarboxylates and the mechanism for this reaction. This paper deals mainly with hydrocarbon phosphoranes and only one fluorinated compound PΪ13P (OCH2CF3)2 was described. The fluorinated compound is prepared either by their new method or reaction of Ph3PBr2 and CF3CH2OH in the presence of Et3N. The later reaction is the same as that used herein. c) D. B. Denney et al., J. Am. Chem. Soc, 103, 1785 (1981) report the preparation of phosphoranes containing trifluoroethoxy group and the reaction of these fluorinated phosphoranes with alkoxides such as trifluoroethoxide. d) T. Kubota et al., J. Org. Chem., 45, 5052 (1980) used bis (2,2,2-trifluoroethoxy)triphenyl- T phosphorane as a condensation reagent for alcohols with thiols. The preparation of PI1 3 P (OCH 2 CF3)2 and application of this reagent in organic synthesis is described in detail. These researchers prepared PI13P (OCH2CF3)2 from the reaction of Ph3PBr2 and NaOCH2CF3 and investigated the reactions of PI13P (OCH2CF3)2 with alcohols, carboxylic acid, thiols and amines. This reference also mentions the reaction of PI13P (OCH2CF3)2 with hydrocarbon aldehydes to give the corresponding acetals. e) Yu. G. Shermalovich et al., Zh. Org. Khim, 52, 2526 (1982) report that (CF3)2C (OCH2CF 2 CF 2 H)2 has been prepared from the reaction of hexafluoroacetone (HFA) and P(OCH 2 CF 2 CF 2 H) 5 . The reaction of (OCH 2 R f ) 5 (R f = ((CF 2 >nH, n = 2,4) with carbonyl compounds is reported. Although the one mentioned fluorinated ketal, (CF3)2C(CH2CF2CF2H)2, was prepared by reaction of P (OCH 2 CF2CF2H) 5 with hexafluoroacetone, the starting material used was different from that used herein; applicant's starting material is PI13P(OCH2R f )2. Applicant believes that the method reported could not be adapted to prepare (CF3) 2 (OCH2CF3)2 by the reaction of HFA with P(OCH2CF 3 ) 5 . SUMMARY OF THE INVENTION Novel triphenylbis (fluoroalkoxy)phosphoranes, 1, Ar 3 P ( OCH 2 Rf ) 2 1 are disclosed. In formula 1, Ar is phenyl (hereinafter Ph) or Ph substituted with alkyl or other substituents that are selected so as not to interfere with the process reaction. R f is a perfluoroalkyl group, a perfluoroalkenyl group or a perfluoroalkynyl group of 1 to 20 carbon atoms, optionally substituted by one or ET more chlorine or hydrogen atoms, and optionally containing one or more oxygen atoms. The perfluoroalkyl group, perfluoroalkenyl group or perfluoroalkynyl group may be straight chain or branched, provided, however, that R f is not CF 3 . Preferred R f groups are selected from the group consisting of CF 2 CI, CF 2 CF 3 , CFCICF 2 CI, and CF 2 =CFOCF 2 CF(CF 3 )OCF 2 CF2. Also disclosed is a process for making fluorinated ketals of the formula 2 from phosphoranes of formula 1 by reaction of these phosphoranes with fluorinated ketones. In formula 2: R f is a perfluoroalkyl group, a perfluoroalkenyl group or a perfluoroalkynyl group of 1 to 20 carbon atoms, optionally substituted by one or more chlorine atoms, and optionally containing one or more oxygen atoms. The perfluoroalkyl group, perfluoroalkenyl group or perfluoroalkynyl group may be straight chain or branched. Preferred R f groups are selected from the group consisting of CF 2 CI, CF2CF3, CFCICF2CI, and CF 2 =CFOCF 2 CF(CF 3 )OCF 2 CF 2 . R f ' is a straight chain or branched perfluoroalkyl group, a perfluoroalkenyl group or a perfluoroalkynyl group of 1 to 20 carbon atoms, optionally substituted by one or more hydrogen atoms and optionally containing one or more oxygen atoms. Preferred R f 1 groups are Ci to C 20 perfluoroalkyl. SUBSTITUTESHEET Especially preferred are CF 3 and CF 2 CF 3 . The process for the preparation of various triphenylbis (fluoroalkoxy)phosphoranes involves the reaction of triphenylphosphine dibromide and the corresponding fluoroalcohols in the presence of a tertiary amine. The triphenylbis (fluoroalkoxy)phosphorane product of this reaction can then be used to prepare fluorinated ketals when reacted with the corresponding ketones, as shown below. wherein R f and R f ' are as defined above. The process can be conducted neat or in the presence of a solvent for one or both of the reagents, within a temperature range of about 20°C to about 250°C. DETAILED DESCRIPTION OF THE INVENTION Although a number of triphenylbis (alkoxy)- phosphoranes, PΪ13P (OCH2R) 2 have been reported in the literature, the preparation of only one triphenylbis- (fluoroalkoxy)phosphorane, PI3P (OCH2CF3) 2, is known. The preparation of this fluorinated phosphorane was achieved by the reaction of PI13P with either CF3CH 2 OH, in the presence of diethyl azodicarboxylate, or trifluoroethyl benzenesulfonate. PI13P (OCH2CF3) 2 can also be prepared by reaction of Ph3PBr2 and NaOCH2CF3. References for these various methods are listed in the Technical Background on page 1, herein. An efficient process for the preparation of various triphenylbis (fluoroalkoxy)phosphoranes involves reaction of triphenylphosphine dibromide and the corresponding fluoroalcohols in the presence of a tertiary amine (e.g., triethylamine) , as shown by the example, below. SUBSTITUTE SHEET where R f is a perfluoroalkyl group, a perfluoroalkenyl group or a perfluoroalkynyl group of 1 to 20 carbon atoms, optionally substituted by one or more chlorine or hydrogen atoms, and optionally containing one or more oxygen atoms. The perfluoroalkyl group, perfluoro¬ alkenyl group or perfluoroalkynyl group may be straight chain or branched. Preferred R f groups are selected from the group consisting of CF2CI, CF2CF3, CFCICF2CI, and CF 2 =CFOCF2CF(CF3)OCF 2 CF2. Et 3 N Ph 3 PBr 2 + R f CH 2 OH ► Ph 3 P(OCH 2 R f ) 2 PI3P (OCH 2 R f ) 2 can then be reacted with the corresponding ketones to produce fluorinated ketals. There appear to be no universal methods for the preparation of fluorinated ketals of the formula (R f ' )2C (OCH2R f ) 2 - As indicated in the Technical Background, above, one fluorinated ketal, (CF3)2C(OCH2CF2CF2H)2, has been reported, which was prepared from the reaction of hexafluoroacetone (HFA) and P (OCH 2 CF 2 CF2H)5. However, that reported method for making (CF3)2C(OCH2CF2CF2H)2 was found not to extend to prepare (CF3)2C(OCH2CF3)2 by the reaction of HFA with P(OCH 2 CF 3 ) 5 . The present process can be carried out neat (no solvent) or in the presence of aprotic solvents such as, but not limited to, dichloromethane, 1, 1,2-trifluoro- trichloroethane, ether, acetonitrile, dimethylformamide (DMF) , benzene, toluene and chlorobenzene. The process is carried on at temperatures from ambient (about 20°C) to about 250°C. A preferred temperature range is about 100°C to about 200°C. It is most preferred to conduct the process at about 150°C to about 200°C. There are no specific pressure requirements. Autogeneous pressure is sufficient. SUBSTITUTESHEET The fluorinated ketals produced are useful synthetic intermediates for fluorocarbon compounds and as monomers for fluoropolymeis . EXAMPLE 1 Synthesis of PI13P (OCH2CF3)2 To a stirred solution of 136.2 g (0.52 mol) of PI13P in 300 mL of of CH2CI2 was added a solution of 41.6 g (0.52 mol) of Br2 in 100 mL of CH2CI2 at -40°C over 1 hour. After the addition was complete, the mixture was stirred at -40°C to room temperature for 1 hour and then cooled to -40°C. A mixture of 100 g (1.0 mol) of CF3CH2OH and 101.0 g (1 mol) of Et3N in 400 mL of ether was added at this temperature over 1 hour and then the resulting reaction mixture was warmed to room temperature and stirred for an additional 3.5 hours. After the solids were removed by filtration under nitrogen, the filtrate was evaporated under vacuum at room temperature to give solids 209.3 g (91%) . Analytic sample was obtained by slow evaporation of CH 2 CI2 and pentane solution, mp 138.4. !H NMR(CDCl 3 ) : 8.11-8.04 (m, 6H) , 7.57-7.33 (m, 9H) , 2.88 (qd, J = 8.9 Hz, J = 4.2 Hz, 4H) ; 19 F NMR(CDCl3) : -74.7 (t, J = 8.9 Hz); 31 P NMR(CH2Cl2) : -58.0 (s) . Calcd. for C22H 1 9F6PO2: C, 57.40; H, 4.16; F, 24.76; P, 6.73. Found: C, 57.27; H, 4.32; F, 24.91; P, 7.06. EXAMPLE 2 Synthesis of PI13P (OCH2CF2CI) 2 A similar experiment using 30.0 g (0.115 mol) of Ph 3 P, 18.3 g (0.115 mol) of Br 2 , 25.0 g (0.21 mol) of C1CF 2 CH 2 0H and 21.2 g (0.21 mol) of Et3N in 100 mL of ether and 100 mL of CH2CI2 gave 50.1 g (96.7%) of Ph 3 P(OCH2CF2Cl) 2 . X H NMR (CDCI3) : 8.14-8.06 (m, 6H) , 7.71-7.49 (m, 9H) , 3.00 (td J = 11.1 Hz, J = 3.8 Hz, 4H) ; 19 F NMR: -61.2 (t, J = 11.0 Hz); 31 P NMR(CH 2 C1 ) : -57.7 (s) . Analytic sample was obtained by slow BSTITUTE SHEET evaporation of solution in CH 2 CI2 and pentane. Calcd. for C22H 1 9F 4 CI2PO2: C, 53.57; H, 3.88; F, 15.41; Cl, 14.3 n ; P, 6.28. Found: C, 53.55; H, 4.19; F, 17.39; Cl, 13.33, P, 6.84. EXAMPLE 3 Synthesis of PI 3P (OCH 2 CF2CF3) 2 A similar experiment using 52.4 g (0.2 mol) of Ph 3 P, 32.0 g (0.2 mol) of Br 2 , 60.0 g (0.4 mol) of CF3CF2CH 2 OH and 41.8 g of Et3N in 150 mL of CH2CI2 and 200 mL of ether gave 105.1 g (94%) of Ph 3 P (OCH 2 CF2CF3) 2 • !H NMR(CDCl3) : 8.07-8.01 (m, 6H) , 7.54-7.33 (m, 9H) , 2.95 (td, J = 13.1 Hz, J = 2.8 Hz, 4H) ; 19 F NMR(CDC1 3 ) : -83.7 (s, 6F), -123.7 (t, J = 13.2 Hz, 4F) ; 31 P NMR(CH 2 Cl2) : -57.2 (s) . EXAMPLE 4 Synthesis of Ph 3 P (OCH2CF2CF2H) 2 A similar experiment using 52.4 g (0.2 mol) of PΪ13P, 32.0 g (0.2 mol) of Br2, 54.1 g (0.41 mol) of HCF2CF2CH2OH and 41.4 g (0.41 mol) of Et3N in 250 mL of CH C1 2 and 250 mL of ether gave 96.6 g (92%) of Ph 3 P(OCH2CF2CF 2 H)2. 1 H NMR(CDCI3) : 8.04-9.76 (m, 4H) , 7.52-7.48 (m, 9H) , 5.74 (tt, J = 53.4 Hz, J = 5.5 Hz, 2H) ; 19 F NMR(CDC1 3 ) : -126.5 (m, 4F) , -141.2 (t, J = 54 Hz, 4F) ; 31 P NMR(CH 2 C1 2 ) : -56.0 (s) . EXAMPLE 5 Synthesis of PI3P (OCH2CFCICF2CI) 2 A similar experiment using 21.0 g (0.08 mol) of PI13P, 12.8 g (0.08 mol) of Br2, 27.0 g (0.147 mol) of CICF2CFCICH2OH and 15.0 g (0.148 mol) of Et3N in 100 mL of CH2CI2 and 100 mL of ether gave 38.1 g (83%) of Ph3P(OCH 2 CFClCF 2 Cl)2. X H NMR (CDCI3) : 8.11-8.03 (m, 6H) , 7.50-7.32 (m, 9H) , 3.11 (dd, J = 24.6 Hz, J = 3.5 Hz, 4H) ; 31 P NMR(CH 2 Cl2) : -56.4 (s) . SUBSTITUTE SHEET EXAMPLE 6 Synthesis of PI13P [OCH2 (CF2) 4H] 2 A similar experiment using 78.6 g (0.3 mol) of PI13P, 48 g (0.3 mol) of Br 2 , 140.0 g (0.6 mol) of H(CF2)4CH2θH and 61.0 g (0.6 mol) of Et3N in 300 mL of CH2CI2 and 300 mL of ether gave 196.7 g (90%) of Ph 3 P[OCH 2 (CF2)4H]2. iH NMR (CDCI3) : 8.09-8.01 (m, 6H) , 7.66-7.47 (m, 9H) , 5.88 (tt, J = 52.0 Hz, J = 5.6 Hz, 2H) , 3.02 (td, J = 14.0 Hz, J = 3.9 Hz); 19 F NMR: -119.7 (t, J = 11.6 Hz, 4F) , -125.8 (s, 4F) , -131.2 (m, 4F), -138.0 (d, J = 52.0 Hz, 4F) ; 31 P NMR(CH Cl2) : -55.5 (s) . EXAMPLE 7 Synthesis of Ph3P ( OCH2CF2CF2θCF2CFCF 3 OCF=CF2)2 A similar experiment using 22.0 g (0.084 mol) of Ph 3 P, 13.4 g (0.084 mol) of Br 2 , 59.5.0 g (0.15 mol) of CF2=CFOCF 2 CF(CF3)OCF 2 CF 2 CH2θH (EVEOH) and 15.2 g (0.15 mol) of Et3N in 100 mL of CH2CI2 and 100 mL of ether gave 59.6 g (75.3%) of Ph 3 P(OEVE)2- 1 H NMR(CDCl3) : 8.08-8.01 (m, 6H) , 7.48-7.32 (m, 9H) , 2.95 (td, J = 13.7 Hz, J = 4.0 Hz, 4H) . 19 F NMR(CDCl3) : -80.3 (s, 6F), -83.9 (m, 4F) , -85.1 (m, 4H) , -113.9 (dd, J = 83.8 Hz, J = 65.6 Hz, 2F) , -122.1 (dd, J = 112.3 Hz, J = 83.8 Hz, 2F), -123.2 (t, J = 13.8 Hz, 4F) , -135.6 (dd, J = 112.3 Hz, J = 65.5 Hz, 2F) , -145.4 (t, J = 21.9 Hz, 2F) . 31 P NMR (CH2C12) : -56.2 (s) . EXAMPLE 8 Synthesis of (CF 3 ) 2 C (OCH2CF3) 2 A solution of 420 g of Ph 3 P (OCH 2 CF 3 ) 2 in 300 mL of CH2CI2 was transferred into a 1 L autoclave under N2 and then pressured with 180 g of hexfluoroacetone . After being heated at 150°C for 3 hours and 200°C for 4 hours, the reaction mixture was poured into a flask and distilled to give the desired product 208.9 g, bp 95.5-96°C, 99.8% purity. 19 F NMR(CDC1 3 ) : -75.1 (t, J = TITUTE SHEET 7.5 Hz, 6F), -76.1 (s, 6F) ; R NMR(CDCl 3 ) : 4.18 (q, J = 7.7 Hz) . Anal: Calcd. for C7H 4 F 12 O 2 : C, 24.15; H, 1.16; F, 65.49. Found: C, 24.21; H, 1.49; F, 65.53. EXAMPLE 9 5 Synthesis of (CF 3 ) 2 C(OCH2CF2CF3) 2 A mixture of 95 g of PΪ13P (OCH2CF2CF3) 2 and 34 g of hexafluoroacetone in 120 L of CH2CI2 was heated in shaker tube at 150°C for 3 hours and at 210°C for 2 hours. Two layers were observed and the lower layer 10 was separated and distilled to give 55.3 g of desired product (99% purity) . bp 120-121°C. 19 F NMR(CDCl3) : -76.0 (s, 6F), -84.4 (s, 6F) , -124.7 (t, J = 11.8 Hz, 4F) ; 1 H NMR(CDCl3) : 4.22 (t, J = 8.0 Hz) , Anal: Calcd. for C9H 4 F16O2: C, 24.12; H, 0.90. Found: C, 15 24.48; H, 1.04. EXAMPLE 10 Synthesis of (CF ) 2 C(OCH2CF2CF2H)2 A mixture of 84 g of Ph 3 P (OCH2CF CF 2 H) and 27 g of hexafluoroacetone in 100 mL of CH2CI 2 was heated in 20 shaker tube at 150°C for 6 hours. After evaporation of the CH2CI2, the residue was distilled under partial vacuum (30 mmHg) to give 56.8 g of crude product (88% purity) . Redistillation gave 36.8 g pure product (99.8% purity), bp 72°C/30 mmHg) . 19 F NMR (CDCI3) : -75.9 25 (s, 6F) , -124.7 (t, J =12.2 Hz, 4F) , -138.4 (d, J = 53.0 Hz, 4F) ; ^-H NMR (CDCI3) : 5.92 (tt, J = 53.0 Hz, J = 3.8 Hz, 2H) , 4.20 (t, J = 12.0 Hz, 4H) . EXAMPLE 11 Synthesis of (CF3CF2)2C(OCH2CF3) 2 30 A mixture of 23 g of Ph 3 P (OCH2CF3)2 and 13.3 g of perfluoropentanone-3 in 30 mL of CH2CI2 was heated in shaker tube at 150°C for 3 hours and 210°C for 3 hours. After evaporation of the CH2CI2, the residue was distilled under partial vacuum (-30 mmHg) to give 7.2 g 35. of crude product. Redistillation gave 6.8 g of pure SUBSTITUTE SHEET product, bp 125-128°C. 19 F NMR(CDCl 3 ) : -74.4 (t, J = 7.5 Hz, 6F), -79.0 (s, 6F) , -117.2 (s, 4F) , ^H NMR (CDCI3) : -4.27 (q, J = 7.6 Hz) . Anal.: Calcd. for C9H4F16O2: C, 24.12; H, 0.90; F, 67.84. Found: C, 24.45; H, 0.95; F, 67.04. EXAMPLE 12 Synthesis of (CF 3 ) 2 C (OCH 2 CF2CF2CF2CF2H)2 A mixture of 74 g of Ph 3 P (OCH2CF 2 CF2CF2CF 2 H)2 containing 16% H(CF 2 ) 4 CH 2 θH and 33.2 g of HFA in 70 mL of CH2CI2 was heated in shaker tube at 150°C for 3 hours and 210°C for 3 hours. After evaporation of the CH2CI2, the residue was distilled to give 28.8 g of product with 89% purity. Redistillation gave 21.0 g of pure product, bp 85°C/5 mmHg. 19 F NMR(CDC1 3 ) : -76.0 (s, 6F) , -121.1 (t, J = 11.6 Hz, 4F), -125.7 (s, 4F) , -130.4 (s, 4F) , -137.8 (d, J = 50.1 Hz, 4F) . Anal: Calcd. for C 1 3H6F22O 2 : C, 25.51; H, 0.99; F, 68.28. Found: C, 25.68; H, 1.05; F, 68.01. EXAMPLE 13 Synthesis of (CF3) 2 C (OEVE) 2 A mixture of 59.6 g of Ph 3 P(OEVE) 2 , 13.0 g of HFA in 30 mL of CH 2 CI2 was heated in shaker tube for 6 hours. The reaction mixture was poured into a jar and the lower layer was separated and distilled under reduced pressure to give 8.5 g of (CF3)2C(OEVE) 2. bp 65-66°C/0.3 mmHg. !H NMR: 4.54 (t, J = 12.4 Hz), 19 F NMR: -75.7 (s, 6F) , -80.0 (f, J = 7.4 Hz, 6F) , -83.3 (in, 4F), -84.7 (m, 4F) , -113.3 (dd, J = 85.0 Hz, J = 65.6 Hz, 2F) , -121.8 (dd, J = 111.8 Hz, J = 85.0 Hz, 2H) , -123.5 (t, J = 12.3 Hz, 4F) , -136.1 (ddt, J = 111.8 Hz, J = 65.5 Hz, J = 5.6 Hz, 2F) , -145.2 (t, J = 21.9 Hz, 2F) . IR (neat) : 2976 (w) , 1839 (m) , 1342 (s) , 1315 (s), 1234 (s) , 1162 (s) . HRMS: Calcd. for C18H4F29O6 (M-CF3) : 867.1826. Found: 866.9549. SUBSTITUTESHEET COMPARATIVE EXAMPLE 1 A. Synthesis of P(OCH 2 CF 3 )s A I L three-necked flask fitted with a mechanical stirrer, a condenser and an addition funnel was charged with 62.6 g of PCI 5 and 600 mL of anhydrous ether. The mixture was cooled at -40°C and a solution of 155 g of CF 3 CH 2 OH, 165 g of Et 3 N in 400 mL of ether was added over 1.5 hours. After the addition was complete, the resulting mixture was stirred at -40°C to room temperature overnight. Solids were removed by filtration under nitrogen and washed with ether. After evaporation of the ether, residue was distilled to give 126.3 g of desired product, bp 81-82°C/9 mmHg. 19 F NMR (CDC13) : -76.0 (t, J = 8.3 Hz); λ H NMR (CDCI 3 ) : 4.20 (qd, J = 7.1 Hz, J = 7.1Hz); 13 C NMR: 123.75 (qd, J = 276.7 Hz, J = 13.0 Hz), 63.38 (qd, J = 36.4 Hz, J = 10.8 Hz). 31 P NMR: -76.3 (s) . B. Reaction of P(OCH 2 CF 3 )s with hexafluoroacetone A mixture of 62.6 g of P(OCH 2 CF 3 )s and 16.6 g of hexafluoroacetone was heated at 150°C in shaker tube for 8 hours. No desired product was obtained and only P(OCH 2 CF 3 ) 5 was recovered. When the above reaction was carried out at 210°C for 8 hours and at 250°C for 5 hours, no reaction was observed. SUBSTITUTESHEET

Claims: WHAT IS CLAIMED IS: 1. A compound of the formula Ar3P (OCH2R f ) 2, wherein Ar is Ph or substituted Ph, and Rf is selected from straight chain or branched perfluoroalkyl, perfluoroalkenyl and perfluoroalkyl, of 1-20 carbon atoms, optionally substituted by one or more chlorine or hydrogen atoms, and optionally containing one or more oxygen atoms, provided, however, that Rf is not CF3. 2. The compound described by Claim 1 wherein Rf is selected from CF2CI, CF2CF3, CFCICF2CI, and CF2=CFOCF 2 CF (CF3) OCF2CF2. 3. A process for making a ketal of the formula: wherein Rf is selected from straight chain or branched perfluoroalkyl, perfluoroalkenyl and perfluoroalkynyl of 1-20 carbon atoms, optionally substituted by one or more chlorine atoms, and optionally containing one or more oxygen atoms and Rf' is a straight chain or branched perfluoroalkyl group, a perfluoroalkenyl group or a perfluoroalkynyl group of 1 to 20 carbon atoms, optionally substituted by one or more hydrogen atoms and optionally containing one or more oxygen atoms, comprising contacting a ketone of the formula wherein Rf' is as defined herein, with a phosphorane of the formula Ar3P (OCH2Rf) 2 wherein Ar is Ph or substituted SUBSTITUTESHEET Ph and R f is as defined herein, said contacting conducted at a temperature from about 20°C to about 250°C. 4. The process of Claim 3 conducted at 100°C to 200°C. 5. The process of Claim 4 conducted at 150°C to 200°C. 6. The process of Claim 3 wherein R f ' is a C to C 20 perfluoroalkyl. 7. The process of Claim 6 wherein R f ' is CF3 or CF2CF3. 8. The process of Claim 3 conducted in the presence of a solvent. 9. The process of Claim 8 conducted in the presence of an aprotic solvent. 10. The process of Claim 9 wherein the solvent is selected from dichloromethylene, 1, 1,2-trifluorotri- chloroethane, ether, acetonitrile, DMF, benzene, toluene and chlorobenzene. 11. The process of Claim 3 conducted at a pressure of about 250 psi . 12. The process described by Claim 3 wherein R f is selected from CF2CI, CF 2 CF3, CFCICF2CI, and CF 2 =CFOCF 2 CF (CF 3 )OCF 2 CF2. 13. A ketal of the formula: wherein R f is selected from straight chain or branched perfluoroalkyl, perfluoroalkenyl and perfluoroalkynyl of 1-20 carbon atoms, optionally substituted by one or more SUBSTITUTE SHEET chlorine, and optionally containing one or more oxygen atoms and R f ' is a straight chain or branched perfluoroalkyl group, a perfluoroalkenyl group or a perfluoroalkynyl group of 1 to 20 carbon atoms, optionally substituted by one or more hydrogen -atoms and optionally containing one or more oxygen atoms. 14. The ketal compound as described by Claim 13 wherein R f is selected from CF 2 CI, CF2CF3, CFCICF 2 CI, and CF 2 =CFOCF 2 CF(CF3)OCF 2 CF 2 . 15. The ketal compound, as described in Claim 13, wherein R f ' is a Ci to C20 perfluoroalkyl. SUBSTITUTE SHEET

Inventors: YANG ZHEN-YU, YANG, ZHEN-YU
Applicants: DU PONT, E.I. DU PONT DE NEMOURS AND COMPANY
Application year: 1994
Main classification: C07F9
IPC codes: C07C41, C07C43, C07F9